Hello, A yearly allocation for the LCRC cluster has been requested with the following updated information: Submitter/PI: hakim iddir Project Name: MBM Division: MSD Project title: Modeling Battery Materials (MBM) Associated funding: EFRC, EERE Other Systems: EMSL-PNNL, CNM-ANL Science: Rechargeable Li-ion batteries (LIB) have become one of the most important energy storage devices for portable electronics, electric and plug-in hybrid vehicles, owing to their high energy density and design flexibility 1. Graphitic based materials are usually used for the anode in commercial LIB because of their low cost, relatively high capacity, non-toxicity, and improved thermal stability and safety over lithium metal anodes2-5, as a result of a passivation film (solid-electrolyte interface (SEI)) that forms on graphite6. Previous studies suggested that defects in disordered/amorphous graphene sheets might be at the origin of their greatly enhanced storage capacity5,7,8. A fundamental understanding of both SEI formation, structure and properties, as well as Li and Li+ diffusion across different defects in graphene planes is a prerequisite to better understand the overall capacity and transport behavior of several graphitic anode materials and configurations in LI B, such as carbon nanospheres 9, carbon nanotubes (CNT)10, highly oriented pyrolitic graphite and graphene paper11. This work will be closely coupled with extensive experimental efforts conducted by two groups from the Chemical Sciences and Engineering (CSE) division, as well as research groups from Northwestern University (NU) and the University of Illinois at Urbana-Champaign (UIUC). This project is being done as part of the ANL EFRC on energy storage and an EERE funded program. (1) Tarascon, J. M.; Armand, M. Nature 2001, 414, 359. (2) Noel, M.; Santhanam, R. Journal of Power Sources 1998, 72, 53. (3) Fauteux, D.; Koksbang, R. Journal of Applied Electrochemistry 1993, 23, 1. (4) Yazami, R.; Touzain, P. Journal of Power Sources 1983, 9, 365. (5) Yoo, E.; Kim, J.; Hosono, E.; Zhou, H.-s.; Kudo, T.; Honma, I. Nano Letters 2008, 8, 2277. (6) Aurbach, D. Journal of Power Sources 2003, 119-121, 497. (7) Pan, D.; Wang, S.; Zhao, B.; Wu, M.; Zhang, H.; Wang, Y.; Jiao, Z. Chemistry of Materials 2009, 21, 3136. (8) Sato, K.; Noguchi, M.; Demachi, A.; Oki, N.; Endo, M. Science 1994, 264, 556. (9) Pol, S. V.; Pol, V. G.; Sherman, D.; Gedanken, A. Green Chemistry 2009, 11, 448. (10) Frackowiak, E.; Béguin, F. Carbon 2002, 40, 1775. (11) Abouimrane, A.; Compton, O. C.; Amine, K.; Nguyen, S. T. The Journal of Physical Chemistry C, 114, 12800. Project description: We propose to investigate the above mentioned properties (SEI formation, structure, Li transport, and reactions at the interface) on model systems using density functional theory (DFT) as implemented in the Vienna Ab Initio Simulation Package (VASP) currently available on FUSION. We have performed several studies of system size/shape dependence Li diffusion through defects in graphite/graphene as well as EC (solvent molecules) interaction with Au(111) and Cu(111) surfaces as part of this project (MBM) using the initial allocated time on Fusion. Recent results suggest that not only EC molecule but reduced (EC+Li) molecule in both open and closed ring configurations should be considered to investigate the SEI growth on Au, Cu and Sn surfaces. Further studies will require adding up to 3 EC (and ECLi) molecules to the most stable adsorbed configurations on Au,Cu and Sn. Frequency calculations will be performed on the resulting most stable configurations to link to the SFG experimental work performed by our EFRC collaborators at UIUC. Also within our EFRC work on battery materials and in collaboration with the experimental group at NU, we will continue to investigate the origin of capacity dependence on the electronic properties of carbon nanotubes (CNT) (We have just started some preliminary calculations on these systems). In this part of the project we will investigate the binding of Li to CNT(20,0) and CNT(11,11) (~1.5 nm diameter 240 and 220 C atoms, respectively) pristine surfaces as well as partially covered CNT surfaces (for example OH) resulting from mild acid treatments of the CNTs. Project URL: Current FY Hours Used: undetermined amount New FY Requested allocation: 800000 Q1: 200000 Q2: 200000 Q3: 200000 Q4: 200000 Justification: The study of solvent molecules interaction with surfaces with frequency calculations will require the investigation of about 20 different configurations per solvent molecule and surface models. For each couple solvent/surface system about 50000 hours would be needed, we anticipate the investigation of EC/Au, EC/Cu, EC/Sn as well as ECLi/Au, ECLi/Cu and ECLi/Sn systems and adding at least one EC (or ECLi) to the most stable configuration for each system above to model the initial SEI growth. We will need about 500000 core hours would be necessary to complete this part of the project. The work on CNTs will require a total of 300000 core hours, Several Li coverage values will be considered (4 values: 0 limit, 0.1, 0.2, 0.5) on each CNT, other configurations of Li inside the CNTs will also be considered. Li binding between Metallic-Semiconducting (M-S), M-M, S-S, CNT pairs will be investigated. A total of about 800000 core hours would be needed to complete this project. Thank You, The LCRC Accounts System